Sulfuric esters of acylated glucamines



nets of the presentinvention methods known to the art.

lions --will 'vary according to 'the United States Patent 2,71 7,3 M Patented Sept. 13, 1955 Fice SULFURIC ESTERS OF ACYLATED .GL'UCAMINES Anthony M. Schwartz, Washington, 'D. (1., assignor to Commercial Solvents Corporation, Terre Haute, Ind., a corporation of Maryland No Drawing. Application May 19, 1951,

Serial No. 227,281 'Cla'ims. (Cl.'260--211) include all those having the structural formula:

wherein R represents a member selected from the group consisting of hydrogen and alkyl radicals having from 1 to 6 carbon atoms inclusive; and R represents the hydrophobic residue of a carboxylic acid having,.8 to carbon atoms inclusive. Specific examples of radicals of the type covered in the definition of R include the straight chain saturated alkyl radicals from C H to C H and the straight chain olefinic radical C H as well as radicals from other carboxylic acids having surface active properties such as, for example, rosin acids, alkylbenzoic acids, alkylphenoxyacetic acids, naphthenic acid, hydroxylated long chain fatty acids such as ricinoleic acids, etc. Specific examples of R include methyl, ethyl, isopropyl, butyl, etc.

Also .included in my invention are the alkali .,met.al, alkaline earth metal, and ammonium salts of .the above described sulfuric esters.

. The starting materials for the-preparation of the prod- N-alkylglucarnines having the "formula:

R'CON-CH;(C'HOH)4-CH2OH :AI wherein R and R'" have the values defined above. These zacyZla ted glucami-ne compounds can "-be iprepared by condens'ing a suitable acid with glucamine -or an N-alkyl- Eglucamine in accordance with "the method described in U. S. Patent No. 1,985,424 issued to Henry Alfred Piggottpor hy condensirrg an aliphaticester-of an acidwith :the g lncamine -or N=zil kylglucamine-as'descfiibedin -my co- "pending application U. Serial No. 164,286, filed May 1 950, now Patent"2,703, 'fl93.

The amides described above are treated with a sulfatirrg agent to produce the sulfate'd amides of my invention. The sulfation maybe carried outby any of the several The sulfating agents and conditions may be chosen according to known'precepts-to give optimum "yields 'of the desired "products. These condiparticular acylated 'g'lucaniine "to be 'sulfated. Among "the "sulfating agents which I have found to be effective in-produc'ing the products ofmy invent-ion aresulfuric acid, sulfuric acid with 'urea, oleum, chlorosulfonic acid, and sulfur 'trioxide. Where thehydrophobicradical contains a isulfatable or sulfonatable grouping, as in the case of oleic, recinoleic or alkoxyacetic derivatives, it is advantageous to use a sulfating agent, sueh-assulfamic acid, which isspecific for primary hydroxyl groups. However, ingeneral I prefer to .carry out the sulfation with cholorosulfonic acid. In accordance withthis method the amide is first dissolved in a so'lventltohomogenize thefinal mixture and to avoid ..an excessively violent reaction.

The solution ,is .then .cooled'to about 30 C. and chlorosulfonieac'id added slowly and with vigorous agitation. The primary product Cal are .acylated ,g'lucamine and Y .base and removing the Cellosolve and the solution cooled to under these conditions is the monosulfate .of the amide and the sulfation takes place almost exclusivelyon the primary .hydroxyl group. It is, however, difiicult to avoid the formation of some product in which two sulfuric .ester groups are present, .one .on the terminal primary .hydroxyl ,group of the glucose residue, as desired, and another on one of the secondary hydroxyl groups. In addition to products :of this nature .there will sometimes be present .in thefinal reaction mixture minor amounts of unsulfated starting material. These products will, in the quantities normally ,present, have little effect on the properties of the main product. The sulfated mixture thus obtained icanheconverted to the alkali metal, alkaline-earth metal, .or ammonium salt by neutralizing with the appropriate solvent.

The preparation {of the products of my invention is further illustrated by the following specific examples.

EXAMPLE I Twenty-three and one-half N-methylglucamide grams .05 mole) of oleic "was dissolved in 75 ml. of diethyl about 30 C. To this solution was added 4 to 5 ml. (.06 to :07 mole) of chlorosulfonic acid, dropw-ise :and with vigorous agitation. The time of addition was about 10 minutes and the temperature rose to about -50 C. The product was isolated by neutralizing with sodium hydroxide and sodium carbonate and separating the solvent by distilla- .tion. it he ;excess inorganic salt was removed ,by extract- ,ing the dried product with hot ethyl .alcohol, in which .the :sulfated fatty acyl glucamides are soluble. The inor-ganic salt is .not soluble in .the hot .ethyl .alcohol .and

was removed by filtration. .Qn evaporating the alcohol from the filtrate, the product was obtained.

Following the procedure given above sulfation of the .-.-ifol1owing amides has been effected:

:Lauric Namethylglucamide *Stearic "N-methylglucamide Palmitic N-methylglucamide .Palmitic glucamide Theilime soap dispersion values for each of the above -sulfated amides was obtained .by the following procedure.

One percent distilled Water solutions were made :up of 'soap and of the sample to be tested. These were mixed in varying proportions, e. g. 20% sample being tested to 80% soap; 10% sample to 90% soap; 6% sample to'94'% soap, etc. Fiveml. of each mixture was diluted with 45 ml. or 400p. p. m. hard Water in a Nessler tube and was then allowed to stand 30 minutes. The mixture of lowest "sample-to-soapratio which'does not form visible agglom- "erates of lime soap under these conditionsrepresents the lime soap dispersion value. Using this procedure, each of the sulfated glucamides prepared as described above gave lime soap dispersion values as low as 0.04. Unsulfatedoleic,Nrrnethylglucamide has a lime soap dispersion value of T0.6,.I1163S1.116d by the above method, .whilepalmitic N-met-hylglucamide has a value of 0.25, lower than any other unsulfated glucamide.

EXAMPLE II :EXAMPLE III The procedure .of Example '11 was repeated with stearic N-methylglucamide. The sodium salt was prepared in the same manner as described in Example I and the product also drum dried.

The products from both Example II and Example III gave clear aqueous solutions of high lime resistance and much better foaming power than the original unsulfated materials. The detergent characteristics of the sodium salts of these products in tap water and in hard water are shown in Tables A and B, below. The detergency test to which these specific compounds were subjected is widely used and well recognized by technologists who have specialized in this field. It consists in washing swatches of standard soiled fabrics under controlled conditions with a standard aqueous solution of the detergent in a Launder-O-Meter instrument, and estimating the degree of soil removal by means of a photometer. In these tests a minute washing interval was used for the cotton swatches and a 10 minute interval was used for the wool. All detergency tests were conducted at C. In the tables, the products are identified by the materials from which they were prepared, thus oleic-MGL stands for oleic N-methylglucamide.

4 EXAMPLE v One mole of the N-methylglucamide of stearic acid was dissolved into ten moles of 95% sulfuric acid and warmed for about 30 minutes to -80" C. The mixture was cooled and neutralized with ice and caustic soda. It was then drum dried, forming a fluffy light tan powder containing approximately 30% of the detergent product and 70% of sodium sulfate. Detergency tests showed that this sulfated product possessed greatly improved cotton detergency and that the wool detergency was not significantly diiferent from the unsulfated material.

EXAMPLE VI One mole of the N-methylglucamide of oleic acid was heated to 7090 C. for 30 minutes with five moles of sulfuric acid to which had been added 20% urea. The sulfating mixture then contained parts 95% sulfuric acid and 20 parts urea. The sulfated product was then cooled and neutralized with ice and caustic soda, to form the sodium salt. Detergency tests also Table A Soil Removal poncentra' Efiiciency, Per- D t t if cent Appearance of {Ki e ergen 0 lVB lIl 0! Tap Water Sohmons Washing (100 Cotton Wool Oleic-M GL 0. 05 7 46 Do 0.1 11 49 Sulfated Oleic-M GL 0. 05 14 48 D0 0.1 16 a1 stearic-M GL 0. 05 3 31 Do 0.1 a 40 Sulfated Stcaric-MGL. 0.05 8 34 Do 0.1 7 36 Table B showed that sulfation by this method improved the cotton detergency. Soi1 Removal I claim: n n m Efliclency, 1. A composition selected from the group consisting Detergent Percent Active cent f a 0 u d h th f 1 laolgiard Wat/e; 0 C mp0 11 aving 6 ormu a.

p. p. m.

Cotton Wool RCON-CHz-(OHOH)4CH1OSO3H Oleic-M GL 0. 05 7 29 8. fig wherein R represents a member selected from the group 13 53 consisting of hydrogen and alkyl radicals having from Do 3- 3 l to 6 carbon atoms inclusive and R represents the hydroa 'iggf gii i'ijjjjj j 05 12 38 phobic residue of a carboxylic acid having 8 to 30 carbon Do 0.1 14 36 atoms inclusive, and the alkali metal, alkaline earth It is apparent from the foregoing tables that the cotton detergency of both products is greatly improved by sulfation, with the effect being more pronounced in hard water than in tap water. Significant improvement in the wool detergency is shown only in hard water. prising since the wool detergency of the original materials is already quite high.

EXAMPLE IV Following the procedure of Example II the following amides have been successfully sulfated by the use of chlorosulfonic acid:

N-isopropylglucamide of cocoanut fatty acids N-isopropylglucamide of oleic acid Glucamide of cocoanut fatty acids N-methylglucamide of lauric acid N-ethylglucamide of palmitic acid N-methylglucamide of myristic acid Tests with the products produced by sulfation of the above amides showed that sulfation improves the solubility, foaming and detergency of the products, especially in hard water. The alkaline earth metal, alkali metal and ammonium salts of these sulfated amides showed outstanding lime soap dispersing properties.

This is not surmetal and ammonium salts of the said compounds.

2. A compound selected from the group consisting of the sulfuric ester of the N-methylglucamide of oleic acid and the alkali metal, alkaline earth metal and ammonium salts of said ester.

3. A compound selected from the group consisting of the sulfuric ester of the N-glucamide of stearic acid and the alkali metal, alkaline earth metal and ammonium salts of said ester.

4. A compound selected from the group consisting of the sulfuric ester of the N-methylglucamide of palmitic acid and alkali metal, alkaline earth metal, and ammonium salts of said ester.

5. A compound selected from the group consisting of the sulfuric ester of the glucamide of cocoanut fatty acids and the alkali metal, alkaline earth metal and ammonium salts of said ester.

References Cited in the file of this patent UNITED STATES PATENTS 1,985,424 Piggott Dec. 25, 1934 2,002,613 Orthner May 28, 1935 2,091,105 Piggott Aug. 24, 1937 2,212,521 Harris Aug. 27, 1940 2,604,467 Crouch et al July 22, 1952 

1. A COMPOSITON SELECTED FROM THE GROUP CONSISTING OF A COMPOUND HAVING THE FORMULA: 